JPS6134745B2 - - Google Patents
Info
- Publication number
- JPS6134745B2 JPS6134745B2 JP12775379A JP12775379A JPS6134745B2 JP S6134745 B2 JPS6134745 B2 JP S6134745B2 JP 12775379 A JP12775379 A JP 12775379A JP 12775379 A JP12775379 A JP 12775379A JP S6134745 B2 JPS6134745 B2 JP S6134745B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- acetate copolymer
- ethylene
- present
- low polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 20
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 18
- 239000005038 ethylene vinyl acetate Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 10
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000004018 acid anhydride group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009503 electrostatic coating Methods 0.000 description 2
- -1 glycidyl ester Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HAZZRKZNTNNBJW-UHFFFAOYSA-N 1-chloro-4-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(Cl)C=C1 HAZZRKZNTNNBJW-UHFFFAOYSA-N 0.000 description 1
- XXTQHVKTTBLFRI-UHFFFAOYSA-N 1-methyl-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C)=C1 XXTQHVKTTBLFRI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Description
本発明は、金属やセラミツクス等に強固に接着
し、耐沸騰水性、機械的強度、硬度、耐溶剤性に
優れた被覆用樹脂組成物に関する。
変性エチレン―酢酸ビニル系共重合体は金属や
セラミツクス等の密着性がよく、機械的強度や透
明性等に優れており、金属やセラミツクス容器へ
の被覆等多くの用途に使用されている。
しかしエチレン―酢酸ビニル共重合体あるいは
変性エチレン―酢酸ビニル系共重合体は、沸騰水
中および温水中で白化し、被着体との密着性およ
び機械的強度が著しく低下するなどの欠点を有し
ている。
このようなことから、本発明者らは上記欠点を
改良すべく鋭意検討の結果、変性エチレン―酢酸
ビニル系共重合体に特定化合物を特定量配合する
ことにより、上記諸欠点が改良され、耐沸騰水
性、機械的強度、硬度、耐溶剤性が著しく向上す
ることを見出し、本発明に至つた。
すなわち本発明は、変性エチレン―酢酸ビニル
系共重合体(A)、無水マレイン酸とスチレン類の低
重合体(B)および１分子中に２ケ以上のエポキシ基
を有するエポキシ樹脂(C)を必須成分とし、その配
合割合（重量比）が(A)：(B)：(C)＝100：１〜40：
５〜20であることを特徴とする被覆用樹脂組成物
を提供するものである。
本発明に使用される変性エチレン―酢酸ビニル
系共重合体(A)は、酢酸ビニル含量が３〜40モル％
のエチレン―酢酸ビニル共重合体もしくはエチレ
ン―酢酸ビニル―不飽和カルボン酸共重合体の(i)
加水分解物または(ii)該加水分解物に更に不飽和カ
ルボン酸をグラフトしたグラフト重合物を意味す
る。上記加水分解物はアセトキシ基の加水分解率
に制限されるものではなく、部分ケン化物あるい
は完全ケン化物を含むが、特に加水分解率が50〜
100％のものが好ましい。ここで不飽和カルボン
酸とは（メタ）アクリル酸で代表され、エチレン
―酢酸ビニル―不飽和カルボン酸共重合体におけ
る（メタ）アクリル酸等の不飽和カルボン酸の含
量は、通常エチレン―酢酸ビニルに対して0.3〜
５重量％である。また、前記グラフト重合物は
（メタ）アクリル酸等の不飽和カルボン酸を、上
記加水分解物に対して0.3〜５重量％グラフト重
合させることにより得られる。
本発明に使用される無水マレイン酸とスチレン
類の低重合体（以下低重合体とする）とは分子
量が1000以下の成分を主成分とするオリゴマーを
意味する。また低重合体におけるスチレン類と
は、一般式
（但し、R1は水素原子または炭素数１〜４の
アルキル基であり、X1，X2は独立に水素原子、
アルキル基、シクロアルキル基、アリール基、ア
ラルキル基又はハロゲン原子を意味する）で表わ
される化合物であり、具体的にはスチレン、α―
メチルスチレン、α，２―ジメチルスチレン、
α，３―ジメチルスチレン、α，４―ジメチルス
チレン、α，２，４―トリメチルスチレン、α―
メチル―４―クロルスチレン等が例示され、これ
らの１種または２種以上が用いられる。
さらに低重合体における無水マレイン酸とし
て、その酸無水物基に一部が一般式
（但し、Y1，Y2はアルコキシル基、水酸基、
アミノ基あるいはハロゲン原子等を表わすが限定
されるものではない）のように変性されたものも
用い得る。なお低重合体は無水マレイン酸とス
チレン類を必須成分とするが、アクリル酸、アク
リル酸エステル等の不飽和モノマーの１種類ある
いは２種以上を更に用いてもさしつかえない。
本発明における低重合体の役割は、酸無水物
基と変性エチレン―酢酸ビニル系共重合体中の水
酸基との反応により架橋反応を起こさせることに
ある。架橋反応には、低重合体中の酸無水物基
が２ケ以上必要であるが酸無水物基が１ケ以下で
ある付加体が入つていても本発明の特徴を損なわ
ない限りさしつかえない。
また、これら樹脂組成物に架橋反応を促進すべ
く触媒の添加および塗膜平滑化のための塗膜流動
調整剤も用い得る。
本発明に使用するエポキシ樹脂とは１分子中に
２ケ以上のエポキシ基を有するものであり、望ま
しくは、融点50〜130℃のグリシジルエーテル型
エポキシ樹脂を使用するが、中でもビスフエノー
ルＡジグリシジルエステル型が一般的である。ま
たグリシジルエーテル型以外のもの、例えばグリ
シジルエステル型やグリシジルアミン型等を併用
しても差支えない。当該樹脂の融点が50℃未満で
あると粉体塗料が貯蔵中ブロツキングを起こし易
く、また130℃を越えると塗料製造時の溶融混練
温度を高くする必要があり、この時に反応が一部
起こるおそれがあつて好ましくない。より好まし
い融点は60〜11℃である。さらに当該エポキシ樹
脂は、平均分子量が800〜4000、エポキシ当量400
〜3000のものが好ましい。
本発明の樹脂組成物は、変性エチレン―酢酸ビ
ニル系共重合体(A)と低重合体との単なる混合物
ではなく、当該変性エチレン―酢酸ビニル系共重
合体と低重合体およびエポキシ樹脂との間に強
固な化学結合が生成していると思われる。すなわ
ち低重合体の一部または全部が、当該変性エチ
レン―酢酸ビニル系共重合体にグラフトまたはブ
ロツク状に結合しており、さらにエポキシ樹脂を
添加するとその全量が前記変性エチレン―酢酸ビ
ニル系共重合体のグラフト物またはブロツク物と
結合し、当該変性エチレン―酢酸ビニル系共重合
体と低重合体からなる組成物にみられない物
性、例えば塗膜硬度が向上する。
本発明で使用される低重合体の添加量は、当
該変性エチレン―酢酸ビニル系共重合体のエチレ
ン含有量、メトルフローインデツクスおよびケン
化度によつては、添加量が多すぎると架橋密度が
大きくなつて溶融粘度が上昇し、平滑な塗膜が得
られなくなる。逆に少ない場合は接着効果がない
ばかりでなく耐溶剤も向上しない。したがつて本
発明の目的とする効果を最大限に発現するために
は低重合体の添加量は変性エチレン―酢酸ビニ
ル系共重合体100重量部あたり１〜40重量部にす
る必要があり、特に５〜20重量部の範囲が好まし
い。
また、本発明で使用されるエポキシ樹脂の添加
量は、変性エチレン―酢酸ビニル系共重合体100
重量部あたり20重量部までは添加量の増加ととも
に耐沸騰水性、耐溶剤性、平滑性、硬度等の性質
が改良されるが、20重量部を越えると耐沸騰水性
は改良されるが衝撃強度、平滑性が低下するとと
もに耐溶剤性が悪くなる。逆に添加量が５重量部
未満では耐沸騰水性、硬度のすぐれた組成物は得
られない。
本発明に使用される低重合体およびエポキシ
樹脂は、前記変性エチレン―酢酸ビニル系共重合
体に対して同時に添加してもよいが両者の添加時
期をずらせるかあるいは、あらかじめそれぞれを
単独に混合した後、それらを再混合せしめる方が
好ましい結果を与える。しかしいずれの方法でも
混合に要する時間は10分以内の極めて短時間であ
るため、工業的に製造する上に非常に有利であ
る。
本発明の樹脂組成物は、通常これらを粉末状に
して使用されるが、その粉末化は、公知の技術で
ある物理的または化学的方法により極めて容易に
かつ工業的に行なうことができる。粉末の粒度お
よび粒度分布は特に規定する理由はなく、これら
は加工の目的、方法および条件ならびに希望する
製品の性質、用途などによつて決定されるが平均
粒度としては30〜300ミクロンのものが好まし
い。
本発明の組成物は、例えば静電塗装法、流動浸
漬法、熔着法あるいはスプレー塗装、デイツピン
グ等の公知の技術によつて金属およびセラミツク
に塗装することが出来る。また本発明の組成物を
粉末、粒状またはフイルム状で用いて押出機、プ
レス、ロール等によつて溶融、圧縮、固化の過程
を経て金属またはセラミツクスとの積層体も製造
することが出来る。この場合、金属の前処理は通
常行なわれている方法、例えばアセトン、トリク
レン等の金属表面の脱脂を行なうことで十分であ
るが更に接着強度の増大を達成するには、クロム
酸塩、リン酸塩等による表面処理を行なうことに
よつて達成出来る。
なお本発明の組成物には、用途に応じてさらに
顔料、体質剤、発泡剤等の添加剤を混合すること
が出来る。
次に実施例を上げて本発明を詳細に説明するが
本発明はこれらに限定されるものではない。
参考例 １
（無水マレイン酸とスチレン類の低重合体の製
造例）
還流コンデンサー、滴下ロ斗、温度計および撹
拌装置のついた１４ツ口フラスコに無水マレイ
ン酸588.4ｇ（6.0モル）を仕込み、昇温溶融し
180℃にした。180℃になつたら予じめ用意してお
いたスチレン182.2ｇ（1.75モル）およびジメチ
ルスチレン※231.4ｇ（1.75モル）の混合液を滴
下ロ斗より８時間で滴下した。滴下中の温度は
180℃〜190℃に保つた。滴下終了後同温度で２時
間保温し、取出した。得られた樹脂は軟化点115
℃の淡い褐色の固体であつた。これを樹脂低重合
体とする。
※ ジメチルスチレンとは、α，４―および
α，２―ジメチルスチレンの混合物でその組
成比は、ほゞ６：４のものである。
また、上記例におけるスチレンおよびジメチル
スチレンにかえて、α―ジメチルスチレン413.7
ｇ（3.5モル）を用いる以外は上記例と同様の操
作をおこない、軟化点110℃の淡い褐色の固体を
得た。これを樹脂低重合体とする。
実施例 １〜５
変性エチレン―酢酸ビニル共重合体、無水マレ
イン酸とスチレン類の低重合体、エポキシ樹脂お
よび顔料を用い、第１表に示す各種配合割合で配
合し、120〜130℃に加温した試験ロール上で10分
間混練してそれぞれペレツト化し、このペレツト
を粉砕機（アルピネ社製、1100回転／分）を用い
て粉砕後、振動篩機にて篩別して200メツシユパ
スのそれぞれの樹脂組成物粉末を得た。次にこの
粉末を使用し、印加電圧70KV、粉体噴出量100
ｇ／分に設定した静電塗装機（ゲマ社製）で物性
測定のための試験片を作製し試験に供した。
比較例 １〜４
第１表に示すごとく変性エチレン―酢酸ビニル
共重合体、無水マレイン酸とスチレン類の低重合
体および顔料系にエポキシ樹脂を添加しない場合
あるいはエポキシ樹脂の添加量を３重量％および
25重量％添加した場合について実施例１〜５と全
く同様の方法で試験片を作製し、同様に物性試験
を供した。
The present invention relates to a coating resin composition that firmly adheres to metals, ceramics, etc., and has excellent boiling water resistance, mechanical strength, hardness, and solvent resistance. Modified ethylene-vinyl acetate copolymers have good adhesion to metals and ceramics, and have excellent mechanical strength and transparency, and are used in many applications such as coating metal and ceramic containers. However, ethylene-vinyl acetate copolymers or modified ethylene-vinyl acetate copolymers have drawbacks such as whitening in boiling water or hot water, and a significant decrease in adhesion to adherends and mechanical strength. ing. In view of this, the present inventors have made extensive studies to improve the above-mentioned drawbacks, and have found that by blending a specific amount of a specific compound into a modified ethylene-vinyl acetate copolymer, the above-mentioned drawbacks have been improved and the durability has been improved. It was discovered that boiling water resistance, mechanical strength, hardness, and solvent resistance were significantly improved, leading to the present invention. That is, the present invention uses a modified ethylene-vinyl acetate copolymer (A), a low polymer of maleic anhydride and styrene (B), and an epoxy resin (C) having two or more epoxy groups in one molecule. It is an essential component, and its blending ratio (weight ratio) is (A):(B):(C)=100:1 to 40:
The object of the present invention is to provide a coating resin composition characterized in that it has a molecular weight of 5 to 20. The modified ethylene-vinyl acetate copolymer (A) used in the present invention has a vinyl acetate content of 3 to 40 mol%.
(i) of ethylene-vinyl acetate copolymer or ethylene-vinyl acetate-unsaturated carboxylic acid copolymer
It means a hydrolyzate or (ii) a graft polymer obtained by further grafting an unsaturated carboxylic acid to the hydrolyzate. The above-mentioned hydrolysates are not limited to the hydrolysis rate of acetoxy groups, and include partially saponified products or completely saponified products, but especially those with a hydrolysis rate of 50 to 50%.
100% is preferred. Here, the unsaturated carboxylic acid is represented by (meth)acrylic acid, and the content of unsaturated carboxylic acids such as (meth)acrylic acid in the ethylene-vinyl acetate-unsaturated carboxylic acid copolymer is usually ethylene-vinyl acetate. 0.3~
It is 5% by weight. Further, the graft polymer can be obtained by graft polymerizing 0.3 to 5% by weight of an unsaturated carboxylic acid such as (meth)acrylic acid to the hydrolyzate. The low polymer of maleic anhydride and styrene used in the present invention (hereinafter referred to as low polymer) means an oligomer whose main component is a component having a molecular weight of 1000 or less. In addition, styrene in low polymers has the general formula (However, R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X 1 and X 2 are independently a hydrogen atom,
alkyl group, cycloalkyl group, aryl group, aralkyl group, or halogen atom), specifically styrene, α-
Methylstyrene, α,2-dimethylstyrene,
α,3-dimethylstyrene, α,4-dimethylstyrene, α,2,4-trimethylstyrene, α-
Examples include methyl-4-chlorostyrene, and one or more of these may be used. Furthermore, as maleic anhydride in low polymers, some of the acid anhydride groups have the general formula (However, Y 1 and Y 2 are alkoxyl groups, hydroxyl groups,
Modified compounds such as amino groups or halogen atoms (including but not limited to) may also be used. The low polymer contains maleic anhydride and styrene as essential components, but one or more unsaturated monomers such as acrylic acid and acrylic esters may also be used. The role of the low polymer in the present invention is to cause a crosslinking reaction by the reaction between the acid anhydride group and the hydroxyl group in the modified ethylene-vinyl acetate copolymer. The crosslinking reaction requires two or more acid anhydride groups in the low polymer; however, it is acceptable even if an adduct having one or less acid anhydride groups is present as long as the features of the present invention are not impaired. . In addition, a catalyst may be added to these resin compositions to promote the crosslinking reaction, and a coating film fluidity regulator may be used to smooth the coating film. The epoxy resin used in the present invention has two or more epoxy groups in one molecule, and preferably a glycidyl ether type epoxy resin with a melting point of 50 to 130°C is used, but among them, bisphenol A diglycidyl Ester type is common. In addition, there is no problem in using in combination other than the glycidyl ether type, for example, the glycidyl ester type and the glycidyl amine type. If the melting point of the resin is less than 50°C, the powder coating is likely to cause blocking during storage, and if it exceeds 130°C, it will be necessary to increase the melting and kneading temperature during paint production, and some reactions may occur at this time. It's hot and undesirable. A more preferable melting point is 60-11°C. Furthermore, the epoxy resin has an average molecular weight of 800 to 4000 and an epoxy equivalent of 400.
~3000 is preferred. The resin composition of the present invention is not just a mixture of a modified ethylene-vinyl acetate copolymer (A) and a low polymer, but also a mixture of the modified ethylene-vinyl acetate copolymer, a low polymer, and an epoxy resin. It seems that a strong chemical bond is formed between them. In other words, part or all of the low polymer is bonded to the modified ethylene-vinyl acetate copolymer in a graft or block form, and when an epoxy resin is further added, the entire amount is bonded to the modified ethylene-vinyl acetate copolymer. It binds to the grafted or blocked material and improves physical properties, such as coating film hardness, which are not seen in the composition composed of the modified ethylene-vinyl acetate copolymer and the low polymer. The amount of the low polymer used in the present invention depends on the ethylene content, mettle flow index, and degree of saponification of the modified ethylene-vinyl acetate copolymer. increases, the melt viscosity increases, and a smooth coating film cannot be obtained. On the other hand, if the amount is too small, not only will there be no adhesive effect, but there will also be no improvement in solvent resistance. Therefore, in order to maximize the desired effect of the present invention, the amount of the low polymer added must be 1 to 40 parts by weight per 100 parts by weight of the modified ethylene-vinyl acetate copolymer. Particularly preferred is a range of 5 to 20 parts by weight. Furthermore, the amount of the epoxy resin used in the present invention is 100% of the modified ethylene-vinyl acetate copolymer.
Up to 20 parts by weight, properties such as boiling water resistance, solvent resistance, smoothness, and hardness will improve as the amount added increases; however, if the amount exceeds 20 parts by weight, boiling water resistance will improve, but impact strength will improve. , the smoothness and solvent resistance deteriorate. Conversely, if the amount added is less than 5 parts by weight, a composition with excellent boiling water resistance and hardness cannot be obtained. The low polymer and epoxy resin used in the present invention may be added to the modified ethylene-vinyl acetate copolymer at the same time, but they should be added at different times or mixed individually in advance. After that, remixing them gives a more favorable result. However, in either method, the time required for mixing is extremely short, less than 10 minutes, which is very advantageous for industrial production. The resin composition of the present invention is usually used in the form of powder, and the powdering can be carried out very easily and industrially by known physical or chemical methods. There is no particular reason to specify the particle size and particle size distribution of the powder, and these are determined by the purpose, method and conditions of processing, as well as the properties and use of the desired product, but the average particle size is 30 to 300 microns. preferable. The composition of the present invention can be applied to metals and ceramics by known techniques such as electrostatic coating, fluidized dipping, fusing, spray coating, and dipping. Furthermore, a laminate with metal or ceramics can be produced by using the composition of the present invention in the form of powder, granules, or film and undergoing melting, compression, and solidification processes using an extruder, press, roll, etc. In this case, it is sufficient to pre-treat the metal using conventional methods such as degreasing the metal surface with acetone, trichlene, etc., but to further increase the bond strength, chromate, phosphoric This can be achieved by surface treatment with salt or the like. In addition, additives such as pigments, extenders, foaming agents, etc. can be further mixed into the composition of the present invention depending on the intended use. Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Reference Example 1 (Production example of a low polymer of maleic anhydride and styrenes) 588.4 g (6.0 mol) of maleic anhydride was charged into a 14-necked flask equipped with a reflux condenser, dropping funnel, thermometer, and stirring device. Melting at elevated temperature
The temperature was set to 180℃. When the temperature reached 180°C, a mixture of 182.2 g (1.75 mol) of styrene and 231.4 g (1.75 mol) of dimethylstyrene* prepared in advance was added dropwise from the dropping funnel over 8 hours. The temperature during dropping is
It was kept at 180℃~190℃. After the dropwise addition was completed, it was kept at the same temperature for 2 hours and then taken out. The resulting resin has a softening point of 115
It was a light brown solid at ℃. This is referred to as a resin low polymer. *Dimethylstyrene is a mixture of α,4- and α,2-dimethylstyrene with a composition ratio of approximately 6:4. Also, instead of styrene and dimethylstyrene in the above example, α-dimethylstyrene 413.7
A pale brown solid with a softening point of 110° C. was obtained by carrying out the same operation as in the above example except using 3.5 mols of g (3.5 mol). This is referred to as a resin low polymer. Examples 1 to 5 A modified ethylene-vinyl acetate copolymer, a low polymer of maleic anhydride and styrenes, an epoxy resin, and a pigment were mixed at various blending ratios shown in Table 1, and heated to 120 to 130°C. They were kneaded for 10 minutes on a heated test roll to form pellets, and the pellets were crushed using a crusher (manufactured by Alpine, 1100 rpm) and then sieved using a vibrating sieve to determine the resin composition of each of the 200 mesh passes. A powder was obtained. Next, use this powder, apply voltage 70KV, powder ejection amount 100
A test piece for measuring physical properties was prepared using an electrostatic coating machine (manufactured by Gema Co., Ltd.) set at g/min and subjected to a test. Comparative Examples 1 to 4 As shown in Table 1, when no epoxy resin is added to the modified ethylene-vinyl acetate copolymer, low polymer of maleic anhydride and styrene, and pigment system, or the amount of epoxy resin added is 3% by weight. and
For the case where 25% by weight was added, test pieces were prepared in exactly the same manner as in Examples 1 to 5, and the physical property tests were conducted in the same manner.
【表】【table】
【表】【table】
Claims (1)
酢酸ビニル共重合体もしくはエチレン―酢酸ビニ
ル―不飽和カルボン酸共重合体の(1)加水分解物ま
たは(2)該加水分解物に更に不飽和カルボン酸をグ
ラフトしたグラフト重合物からなる変性エチレン
―酢酸ビニル共重合体(A)、無水マレイン酸とスチ
レン類の低重合体(B)および１分子中に２ケ以上の
エポキシ基を有するエポキシ樹脂(C)を必須成分と
し、その配合割合（重量比）が(A)：(B)：(C)＝
100：１〜40：５〜20であることを特徴とする被
覆用樹脂組成物。1 Ethylene with a vinyl acetate content of 3 to 40 mol%
Modified ethylene consisting of (1) a hydrolyzate of a vinyl acetate copolymer or an ethylene-vinyl acetate-unsaturated carboxylic acid copolymer, or (2) a graft polymer obtained by grafting an unsaturated carboxylic acid to the hydrolyzate. The essential components are a vinyl acetate copolymer (A), a low polymer of maleic anhydride and styrene (B), and an epoxy resin having two or more epoxy groups in one molecule (C). ratio) is (A):(B):(C)=
A coating resin composition characterized in that the ratio is 100:1 to 40:5 to 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12775379A JPS5650941A (en) | 1979-10-02 | 1979-10-02 | Covering resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12775379A JPS5650941A (en) | 1979-10-02 | 1979-10-02 | Covering resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5650941A JPS5650941A (en) | 1981-05-08 |
| JPS6134745B2 true JPS6134745B2 (en) | 1986-08-09 |
Family
ID=14967827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12775379A Granted JPS5650941A (en) | 1979-10-02 | 1979-10-02 | Covering resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5650941A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5864259A (en) * | 1981-10-09 | 1983-04-16 | 電気化学工業株式会社 | Thermosettable resin composition and manufacture of metal coated laminate board therewith |
| JPS6087751A (en) * | 1983-10-20 | 1985-05-17 | House Food Ind Co Ltd | Production of retort bean curd |
| JPS62163666A (en) * | 1986-01-14 | 1987-07-20 | Kikkoman Corp | Grinding of soybean |
| US5344883A (en) * | 1992-10-05 | 1994-09-06 | Alliedsignal Inc. | Polymeric powder coating compositions comprising low molecular weight copolymer or terpolymer salts of α-olefins and α,β-ethylenically unsaturated carboxylic acids |
| US5470912A (en) * | 1993-03-08 | 1995-11-28 | Alliedsignal Inc. | Polymeric powder coating compositions comprising low molecular weight polyethylene polyols |
| KR100546769B1 (en) * | 1999-02-04 | 2006-01-26 | 제일모직주식회사 | Thermoplastic resin composition with good grease resistance |
-
1979
- 1979-10-02 JP JP12775379A patent/JPS5650941A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5650941A (en) | 1981-05-08 |
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